EP3525043B1 - Verfahren für die herstellung von tonern mit reduzierten emissionen von ultrafeinen partikeln (ufp) - Google Patents

Verfahren für die herstellung von tonern mit reduzierten emissionen von ultrafeinen partikeln (ufp) Download PDF

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Publication number
EP3525043B1
EP3525043B1 EP19155621.6A EP19155621A EP3525043B1 EP 3525043 B1 EP3525043 B1 EP 3525043B1 EP 19155621 A EP19155621 A EP 19155621A EP 3525043 B1 EP3525043 B1 EP 3525043B1
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Prior art keywords
toner
wax
particles
temperature
poly
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French (fr)
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EP3525043A1 (de
Inventor
Siddhesh Nitin Pawar
Juan A. Morales-Tirado
Grazyna E. Kmiecik-Lawrynowicz
Daniel W. Asarese
Jordan A. Frank
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Xerox Corp
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Xerox Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/09392—Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0808—Preparation methods by dry mixing the toner components in solid or softened state
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0815—Post-treatment
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08704—Polyalkenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08726—Polymers of unsaturated acids or derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08786—Graft polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/09307—Encapsulated toner particles specified by the shell material
    • G03G9/09314—Macromolecular compounds
    • G03G9/09321—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • Ultrafine particles are typically characterized as nanoparticles having sizes of 100 nm or less.
  • Xerographic printing devices can be a source of UFP emissions during normal operation.
  • sources of the UFP emissions including toner components, fuser roll lubricants or oils, paper, and plasticizers from plastic materials that constitute the main body of the device.
  • Conventional approaches to reducing UFP emission have focused on lowering the fusing temperature of xerographic printing devices.
  • the present disclosure provides a method of forming of toners exhibiting reduced emission of ultrafine particles (UFPs).
  • the present invention relates to a method of forming a toner as defined in claim 1.
  • Preferred embodiments of the present invention are defined in the sub-claims.
  • FIG. 1 shows a plot of particle count versus temperature for a number of toners, each toner having a different type of wax and/or an amount of wax.
  • the present disclosure provides toners exhibiting reduced emission of ultrafine particles (UFPs) and related methods.
  • UFPs ultrafine particles
  • the toners obtained by the present disclosure result in significantly lower UFP emissions when used in xerographic printing devices as compared to their associated comparative toners (e.g., in embodiments, more than 5 times less).
  • the toners obtained by the present disclosure exhibit the same fusing properties as their associated comparative toners.
  • the toners obtained by the present disclosure comprise at least one resin, at least one wax, and optionally, at least one colorant.
  • the toners may be core-shell toners.
  • the toners may be compared to comparative toners.
  • comparative toner it is meant that the composition of the toner and the composition of its comparative toner are the same, except for the waxes of the toner and the comparative toner, which are different.
  • the type of wax, the amount of wax, or both may be different in the toner as compared to its comparative toner.
  • composition refers to the other toner components as well as the amounts of those components.
  • component/amounts/processes it is meant that the process of preparing the toner and its comparative toner is the same.
  • the term “same” is meant to encompass identical components/amounts/processes as well as components/amounts/processes which may deviate slightly from being identical, but that the deviation is too small to affect the properties of the toner.
  • Example 3 may be considered to be a toner of the present disclosure while Example 1 may be considered to be its associated comparative toner.
  • Example 4 may be considered to be a toner of the present disclosure while Example 1 may be considered to be its associated comparative toner.
  • resins may be utilized in the toners obtained by the present disclosure.
  • Such resins may be made from any suitable monomers, depending upon the particular polymer to be utilized. Suitable monomers include, but are not limited to styrenes, acrylates, methacrylates, butadienes, isoprenes, acrylic acids, methacrylic acids, acrylonitriles, mixtures thereof, and the like.
  • resins examples include polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, and the like, as well as mixtures thereof.
  • resins which can be used include poly(styrene-acrylate) resins, crosslinked poly(styrene-acrylate) resins, poly(styrene-methacrylate) resins, crosslinked poly(styrene-methacrylate) resins, poly(styrene-butadiene) resins, crosslinked poly(styrene-butadiene) resins, polyester resins, alkali sulfonated-polyester resins, branched alkali sulfonated-polyester resins, alkali sulfonated-polyimide resins, branched alkali sulfonated-polyimide resins, alkali sulfonated poly(styrene-acrylate) resins, crosslinked alkali sulfonated poly(styrene-acrylate) resins, poly(styrene-methacrylate) resins, crosslinked alkali s,
  • Examples of other resins include poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene),
  • Examples of other resins include poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly (styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly (styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(alkyl acrylate-butylacrylate-acrylonit
  • the polymers of the resin can be block, random, or alternating copolymers, as well as combinations thereof.
  • the resin is a styrene/n-butylacrylate/ ⁇ -carboxyethylacrylate copolymer wherein the molar ratio of monomers is from about 69 to about 90 parts styrene, from about 9 to about 30 parts n-butylacrylate, and from about 1 to about 10 parts ⁇ -carboxyethylacrylate, wherein the weight average molecular weight (M w ) value is from about 30,000 to about 40,000, and wherein the number average molecular weight (M n ) value is from about 8,000 to about 15,000.
  • Both the M w and the M n may be determined using Gel Permeation Chromatography (GPC).
  • the resin has a glass transition temperature (T g ) in the range of from about 35 °C to about 75 °C, from about 40 °C to about 70 °C, or from about 45 °C to about 65 °C.
  • T g may be determined using Differential Scanning Calorimetry (DSC).
  • any of the resins described above may be utilized as a latex.
  • Such latexes may be prepared utilizing any of the monomers described above in various amounts, depending upon the resin(s) to be utilized.
  • a variety of emulsion polymerization processes may be used to form such latexes, including semi-continuous emulsion polymerization.
  • a variety of different types of surfactants, initiators, chain transfer agents, crosslinking agents, stabilizers, and combinations thereof, in various amounts, may be used in the processes for forming such latexes.
  • the latexes described above may be utilized to form the toners obtained by the present disclosure.
  • the toners include a wax and may include other components, such as a colorant.
  • Such waxes and colorants may be utilized in dispersions containing a surfactant.
  • a variety of different types of surfactants and combinations of surfactants may be used, including anionic, cationic and nonionic surfactants.
  • At least one wax is included in the toner, wherein the at least one wax is characterized by a T m which is at least 90 °C and the amount of the at least one wax is no more than 10% by weight of the toner.
  • a function of the wax is to provide a release function to minimize the adhesion of the toner layer to the fuser roll during the fusing step. Selection of the wax(es) and the amount of wax(es) in the toner is based, in part, on achieving this release function. However, in the present disclosure, the type of wax(es) and the amount of wax(es) are also selected to suppress the emission of ultrafine particles (UFPs) from the toner, e.g., when being used in a xerographic printing device.
  • UFPs ultrafine particles
  • the type of wax(es) and the amount of the wax(es) may be selected to achieve a predetermined T UFP onset value (the temperature at which particle count begins to rise above zero) and/or a predetermined PER 10 value (the total count of ultrafine particles emitted in a 10 minute print phase of a xerographic printing device).
  • a "predetermined" value refers to the desired value to be obtained as determined prior to formation of the toner.
  • the type and amount of the wax(es) in the toner may also be selected to ensure a particular fusing property (as further described below).
  • the wax(es) used in the toners of the present disclosure have relatively high melting temperatures (T m ), e.g., as compared to the wax(es) of their associated comparative toners.
  • T m melting temperatures
  • the wax(es) of the toner is characterized by a T m which is at least 13 °C, at least 15 °C, or at least 17 °C greater than the T m of the wax(es) of its associated comparative toner.
  • the wax(es) of the toner is characterized by a T m of at least 90 °C, or at least 93 °C.
  • an illustrative wax which may be used is a polymethylene wax dispersion (e.g., polymethylene wax dispersions available from Cytech Products).
  • Another illustrative wax which may be used is a montanic acid ester wax (e.g., Licowax WE4, WE40, or WM31 available from Clariant).
  • An illustrative wax which may be used is a polyethylene wax dispersion (e.g., D1509 available from Omnova).
  • the toner comprises a single wax (i.e., only one type of wax).
  • the wax(es) used in the toners of the present disclosure are present in amounts which are relatively small, e.g., as compared to the amount of wax(es) in their associated comparative toners.
  • the toner contains at least 16% less total wax as compared to its associated comparative toner. This includes embodiments in which the toner contains at least 18% less total wax or at least 20% less total wax as compared to its comparative toner.
  • the wax(es) is present in the toner in an amount of no more than 10% by weight of the toner, no more than 9% by weight of the toner, in the range of from 1% to 10% by weight of the toner, from 2% to 10% by weight of the toner, or from 5% to 10% by weight of the toner.
  • the wax of the comparative toner is a paraffin wax, e.g., a paraffin wax having a T m of 75 °C. In embodiments, the wax of the comparative toner is present in an amount of about 11% by weight of the comparative toner.
  • a colorant may be included in the toners obtained by the present disclosure.
  • Colorants include, for example, pigments, dyes, mixtures thereof, such as mixtures of dyes, mixtures of pigments, mixtures of dyes and pigments, and the like.
  • the colorant may be added in amounts sufficient to impart the desired, color, hue, shade, and the like.
  • the colorant may be present in an amount of, for example, from about 0% to about 20% by weight of the toner, from about 1% to about 15% by weight of the toner, or from about 2% to about 10% by weight of the toner.
  • Carbon black which is available in forms, such as furnace black, thermal black, and the like is a suitable colorant. Carbon black may be used with one or more other colorants, such as a cyan colorant, to produce a desired hue.
  • cyan pigments include copper tetra(octadecylsulfonamido) phthalocyanine, a copper phthalocyanine colorant listed in the Color Index (CI) as CI 74160, HELIOGEN BLUE L6900 TM , D6840 TM , D7080 TM , D7020 TM , PYLAM OIL BLUE TM , PYLAM OIL YELLOW TM and PIGMENT BLUE I TM available from Paul Uhlich & Co., Inc., CI Pigment Blue (PB), PB 15:3, PB 15:4, an Anthrazine Blue colorant identified as CI 69810, Special Blue X-2137, mixtures thereof, and the like.
  • CI Color Index
  • magenta pigments examples include a diazo dye identified as C.I. 26050, 2,9-dimethyl-substituted quinacridone, an anthraquinone dye identified as C.I. 60710, C.I. Dispersed Red 15, CINQUASIA MAGENTA TM available from E.I. DuPont de Nemours & Co., C.I. Solvent Red 19, Pigment Red (PR) 122, PR 269, PR 185, mixtures thereof, and the like.
  • diazo dye identified as C.I. 26050, 2,9-dimethyl-substituted quinacridone
  • an anthraquinone dye identified as C.I. 60710
  • C.I. Dispersed Red 15 CINQUASIA MAGENTA TM available from E.I. DuPont de Nemours & Co.
  • C.I. Solvent Red 19 Pigment Red (PR) 122, PR 269, PR 185, mixtures thereof, and the
  • yellow colorants include diarylide yellow 3,3-dichlorobenzidene acetoacetanilide, a monoazo pigment identified in the Color Index as C.I. 12700, C.I. Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, LEMON CHROME YELLOW DCC 1026 TM CI, NOVAPERM YELLOW FGL TM from sanofi, Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (sanofi), Permanent Yellow YE 0305 (Paul Uhlich), Pigment Yellow 74, Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), SUCD-Yellow D1355 (BASF), Permanent Yellow FGL, Disperse Yellow, 3,2,5-dimeth
  • the toners obtained by the present disclosure may be prepared by any method within the purview of one skilled in the art. Although embodiments relating to toner preparation are described below with respect to emulsion-aggregation (EA) processes, any suitable method of preparing toner may be used, including chemical processes, such as suspension and encapsulation processes.
  • the toners are prepared by EA processes, such as a process that includes aggregating a mixture of a wax, a latex containing a resin, and optionally, a colorant to form aggregated particles, and then coalescing the aggregated particles.
  • the process may involve homogenization, e.g., by mixing at about 600 to about 6,000 revolutions per minute.
  • the wax may be added through a homogenization loop.
  • An aggregating agent may be added to the mixture of the wax, the latex and optionally, the colorant. Any suitable aggregating agent may be utilized.
  • the aggregating agent may be an inorganic cationic coagulant, such as, for example, a polyaluminum halide, such as polyaluminum chloride (PAC) or the corresponding bromide, fluoride or iodide; a polyaluminum silicate, such as, polyaluminum sulfosilicate (PASS); or a water soluble metal salt, including, aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulf
  • the aggregating agent may be added to the mixture in various amounts.
  • the amount of aggregating agent is from about 0.1% to about 8% by weight of the mixture, from about 0.2% to about 5% by weight of the mixture, or from about 0.5% to about 2% by weight of the mixture.
  • the aggregating agent may be added in a solution of nitric acid or a similar acid.
  • the aggregating agent may be metered into the mixture over time. The addition of the aggregating agent may be accomplished with continued homogenization. The mixture may be further homogenized after addition.
  • the particles in the mixture may be permitted to aggregate until a predetermined particle size is obtained.
  • a predetermined size refers to the desired particle size to be obtained as determined prior to formation, and the particle size may be monitored during the growth process. Samples may be taken during the growth process and analyzed, for example, with a Coulter Counter. Once the predetermined desired particle size is reached, the growth process is halted.
  • the volume average particle diameter of the aggregated particles may be, for example, from about 3 ⁇ m to about 10 ⁇ m, in embodiments, from about 5 ⁇ m to about 9 ⁇ m, or from about 6 ⁇ m to about 8 ⁇ m.
  • a resin coating may be applied to the aggregated particles to form a shell thereover.
  • Any resin described above may be utilized for the shell.
  • the resin utilized for the shell contains a styrene-alkyl acrylate- ⁇ -CEA copolymer.
  • the resin is a styrene/n-butylacrylate/ ⁇ -carboxyethylacrylate copolymer, including a styrene/n-butylacrylate/ ⁇ -carboxyethylacrylate copolymer having the characteristics described above.
  • the resin in the core and the resin in the shell need not be the same.
  • the shell resin may be utilized in the form of a latex as described above.
  • the pH of the mixture may be adjusted with a pH control agent to a value of, for example, from about 3 to about 10, in embodiments from about 4 to about 9, or from about 4 to about 6.
  • Suitable pH control agents include various bases including alkali metal hydroxides such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, and the like.
  • a chelating agent such as ethylenediaminetetraacetic acid (EDTA) or salts of EDTA may be added to help adjust the pH to the desired value.
  • the temperature of the mixture may be raised, e.g., to a desired coalescence temperature and the pH of the mixture may be adjusted to a desired coalescence pH by adding an aqueous acid solution, e.g., HNO 3 .
  • the particles may then be coalesced to the desired final shape, the coalescence being achieved, by, for example, heating/maintain the temperature of the mixture at a temperature of from about 80° C. to about 110° C., in embodiments from about 85° C. to about 100° C., which may be at or above the T g of the resin(s) utilized to form the toner particles.
  • the particular selection of temperature is a function of the resins used.
  • Coalescence may be accomplished over a period of time, for example, of from about 1 minute to about 10 hours or from about 5 minutes to about 5 hours.
  • the particles may be coalesced until a desired circularity is achieved.
  • pH control agents may be used to adjust the pH, for example, to a value of from about 3 to about 10, in embodiments from about 5 to about 10, or from about 5 to about 7.
  • the mixture may be cooled to room temperature.
  • the cooling may be rapid or slow as desired.
  • pH control agents may be used to adjust the pH, for example, to a value of from about 3 to about 10, in embodiments, from about 4 to about 9, or from about 6 to about 9.
  • the toner particles may be sieved, washed, and then dried.
  • the toner particles may contain various total amounts of resin, for example, in an amount of from about 60% to about 95% by weight of the toner, from about 65% to about 90% by weight of the toner, or from about 75% to about 85% by weight of the toner.
  • the toner obtained by the present disclosure may further contain a variety of additives to enhance the properties of the toner.
  • Charge additives may be present in amounts of, for example, from about 0.1% to about 10% by weight of the toner or from about 0.5% to about 7% by weight of the toner.
  • Suitable charge additives include alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493 ; 4,007,293 ; 4,079,014 ; 4,394,430 and 4,560,635 negative charge enhancing additives like aluminum complexes, any other charge additives, mixtures thereof, and the like.
  • the toner obtained by the present disclosure may contain surface additives.
  • Surface additives that can be added to the toner particles after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silicas, metal oxides, strontium titanates, mixtures thereof, and the like, which each may be present in an amount of from about 0.1% to about 10% by weight of the toner or from about 0.5% to about 7% by weight of the toner. Examples of such additives include, for example, those disclosed in U.S. Pat. Nos. 3,590,000, 3,720,617 , 3,655,374 and 3,983,045 .
  • Other additives include zinc stearate and AEROSIL R972 ® available from Degussa.
  • coated silicas of U.S. Pat. No. 6,190,815 and U.S. Pat. No. 6,0004,714 can also be selected in amounts, for example, of from about 0.05% to about 5% by weight of the toner or from about 0.1% to about 2% by weight of the toner, which additives can be added during the aggregation process or blended into the formed toner particles.
  • particles of dry toner, exclusive of external surface additives have the following characteristics:
  • the volume average particle diameter may be measured by a Beckman Coulter Multisizer 3, operated in accordance with the manufacturer's instructions. Representative sampling may occur as follows: a small amount of toner sample, about 1 gram, may be obtained and filtered through a 25 ⁇ m screen, then put in isotonic solution to obtain a concentration of about 10%, with the sample then run in the Beckman Coulter Multisizer 3. The circularity may be determined using a FPIA-Sysmex 3000. The T g may be determined using DSC.
  • the toner obtained by the present disclosure is a toner which exhibits reduced UFP emission, e.g., as compared to an associated comparative toner.
  • UFP emission may be quantified by one or more of a T UFP onset value (the temperature at which particle count begins to rise above zero) and a PER 10 value (the total count of ultrafine particles emitted in a 10 minute print phase of a xerographic printing device). Measurement of both these values is described in detail in the Examples, below.
  • reference to a "measured T UFP onset value" and a "measured PER 10 value” means a measurement as described in the Examples, below.
  • the toner obtained by the present disclosure may be designed (e.g., by selection of wax type/amount) to achieve a predetermined T UFP onset value and/or a predetermined PER 10 value.
  • the predetermined T UFP onset value is at least 165 °C, at least 170 °C, or at least 175 °C.
  • the measured T UFP onset value of the toner is generally equal to, but may be greater than the predetermined T UFP onset value.
  • the toners of the present disclosure are characterized by measured T UFP onset values which are greater than those of their associated comparative toners.
  • the toner is characterized by a measured T UFP onset value which is at least 10 °C, at least 13 °C, or at least 16 °C greater than its associated comparative toner.
  • the PER 10 value is no more than 1 ⁇ 10 11 particles/cm 3 .
  • the toners obtained by the present disclosure are characterized by measured PER 10 values which are less than those of their associated comparative toners.
  • the toner is characterized by a measured PER 10 value which is at least 2 times less, at least 3 times less, or at least 5 times less than its associated comparative toner.
  • the toners obtained by the present disclosure exhibit higher (lower) measured T UFP onset values (PER 10 values) as compared to their associated comparative toners
  • the toners and their associated comparative toners exhibit the same fusing performance as reflected by one or more of Minimum Fix Temperature (MFT) and Hot Offset Temperature (HOT). These properties may be measured according to the techniques described in the Examples, below.
  • MFT Minimum Fix Temperature
  • HAT Hot Offset Temperature
  • the toners, inclusive of external surface additives exhibit a MFT in the range of from 145 °C to 156 °C, from 150 °C to 156 °C, or from 152 °C to 155 °C. In embodiments, the toners, inclusive of external additives, exhibit a HOT of greater than 195 °C.
  • the toners obtained by the present disclosure may be formulated into developer compositions.
  • Developer compositions can be prepared by mixing the toners of the present disclosure with known carrier particles, including coated carriers, such as steel, ferrites, and the like.
  • carrier particles include those disclosed in U.S. Pat. Nos. 4,937,166 and 4,935,326 .
  • the carriers may be present from about 2% to about 8% by weight of the toner or from about 4% to about 6% by weight of the toner.
  • the carrier particles can also include a core with a polymer coating thereover, such as polymethylmethacrylate (PMMA), having dispersed therein a conductive component like conductive carbon black.
  • PMMA polymethylmethacrylate
  • Carrier coatings include silicone resins such as methyl silsesquioxanes, fluoropolymers such as polyvinylidiene fluoride, mixtures of resins not in close proximity in the triboelectric series such as polyvinylidiene fluoride and acrylics, thermosetting resins such as acrylics, mixtures thereof and other known components.
  • silicone resins such as methyl silsesquioxanes
  • fluoropolymers such as polyvinylidiene fluoride
  • mixtures of resins not in close proximity in the triboelectric series such as polyvinylidiene fluoride and acrylics
  • thermosetting resins such as acrylics, mixtures thereof and other known components.
  • the toners obtained by the present disclosure may be used in a variety of xerographic printing processes using a variety of xerographic printing devices.
  • a xerographic printing process may include forming an image with a xerographic printing device including a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fusing component.
  • the development component may include a developer prepared by mixing a carrier with any of the toners described herein.
  • the xerographic printing device may include a high-speed printer, a black and white high-speed printer, a color printer, and the like.
  • the image may then be transferred to an image receiving medium such as paper and the like.
  • a suitable image development method e.g., magnetic brush development, jumping single component development, hybrid scavengeless development (HSD) and the like
  • the image may then be transferred to an image receiving medium such as paper and the like.
  • any of the toners may be used in developing an image by utilizing a fuser roll member.
  • Fuser roll members are contact fusing devices that are within the purview of those skilled in the art, in which heat and pressure from the roll may be used to fuse a toner to the image receiving medium.
  • the fuser member may be heated to a temperature above the fusing temperature of the toner, for example to temperatures of from about 70° C. to about 160° C., from about 80° C. to about 150° C., or from about 90° C. to about 140° C., after or during melting onto the image receiving substrate.
  • room temperature refers to a temperature of from about 20° C. to about 25° C.
  • toners were prepared as described in Examples 1-5, below. In each case, particles size was determined using a Beckman Coulter Multisizer III and circularity was determined using a FPIA-Sysmex 3000.
  • a toner was prepared by an emulsion aggregation process.
  • a reactor was initially charged with 29.6 kg of de-ionized water, 13.4 kg of a styrene-butyl acrylate resin in a latex emulsion, 0.71 kg of a Cyan pigment dispersion, and 1.36 kg of a carbon black pigment dispersion.
  • the wax dispersion was added through a homogenization loop to assure that larger agglomerates were broken down into smaller sized particles.
  • the wax dispersion and agglomerating agent solution were added to the reactor, all of the components in the reactor were homogenized for 10 min or until the size of the particles in the dispersion was less than 3 ⁇ m.
  • the mixture was aggregated for approximately 110 min until the mean aggregate size reached 6.9 ⁇ m.
  • the shell resin an additional 7.69 kg of a styrene-butyl acrylate resin in a latex emulsion
  • the growth of the particles was stopped by the addition of sodium hydroxide until the slurry reached a pH of about 5.5. Then, the batch target temperature was raised to 96 °C.
  • downstream operations included sieving of the slurry to remove the oversize particles that may have been formed due to the high temperature in the reactor, washing the particles to remove surfactants or other ionic species that may impart undesired charging properties, and removing excess moisture by drying the particles.
  • the dry particles were then blended with various surface additives to impart the desired charging characteristics of the toner.
  • a toner was prepared by an emulsion aggregation process.
  • a reactor was initially charged with 29.6 kg of de-ionized water, 14.0 kg of a styrene-butyl acrylate resin in a latex emulsion, 0.71 kg of a Cyan pigment dispersion, and 1.36 kg of a carbon black pigment dispersion.
  • the wax dispersion was added through a homogenization loop to assure that larger agglomerates were broken down into smaller sized particles.
  • the wax dispersion and agglomerating agent solution were added to the reactor, all of the components in the reactor were homogenized for 10 min or until the size of the particles in the dispersion was less than 3 ⁇ m.
  • the mixture was aggregated for approximately 110 min until the mean aggregate size reached 6.9 ⁇ m.
  • the shell resin an additional 7.69 kg of a styrene-butyl acrylate resin in a latex emulsion
  • the growth of the particles was stopped by the addition of sodium hydroxide until the slurry reached a pH of about 5.5. Then, the batch target temperature was raised to 96 °C.
  • downstream operations included sieving of the slurry to remove the oversize particles that may have been formed due to the high temperature in the reactor, washing the particles to remove surfactants or other ionic species that may impart undesired charging properties, and removing excess moisture by drying the particles.
  • the dry particles were then blended with various surface additives to impart the desired charging characteristics of the toner.
  • the surface additives used were the same as those used in Example 1.
  • a toner particle was prepared by an emulsion aggregation process.
  • a reactor was initially charged with 29.3 kg of de-ionized water, 13.4 kg of a styrene-butyl acrylate resin in a latex emulsion, 0.71 kg of a Cyan pigment dispersion, and 1.36 kg of a carbon black pigment dispersion.
  • the wax dispersion was added through a homogenization loop to assure that larger agglomerates were broken down into smaller sized particles.
  • the wax dispersion and agglomerating agent solution were added to the reactor, all of the components in the reactor were homogenized for 10 min or until the size of the particles in the dispersion was less than 3 ⁇ m.
  • the mixture was aggregated for approximately 110 min until the mean aggregate size reached 6.9 ⁇ m.
  • the shell resin an additional 7.69 kg of a styrene-butyl acrylate resin in a latex emulsion
  • the growth of the particles was stopped by the addition of sodium hydroxide until the slurry reached a pH of about 5.5. Then, the batch target temperature was raised to 96 °C.
  • downstream operations included sieving of the slurry to remove the oversize particles that may have been formed due to the high temperature in the reactor, washing the particles to remove surfactants or other ionic species that may impart undesired charging properties, and removing excess moisture by drying the particles.
  • the dry particles were then blended with various surface additives to impart the desired charging characteristics of the toner.
  • the surface additives used were the same as those used in Example 1.
  • a toner was prepared by an emulsion aggregation process.
  • a reactor was initially charged with 29.5 kg of de-ionized water, 13.4 kg of a styrene-butyl acrylate resin in a latex emulsion, 0.71 kg of a Cyan pigment dispersion, and 1.36 kg of a carbon black pigment dispersion.
  • the wax dispersion was added through a homogenization loop to assure that larger agglomerates were broken down into smaller sized particles.
  • the wax dispersion and agglomerating agent solution were added to the reactor, all of the components in the reactor were homogenized for 10 min or until the size of the particles in the dispersion was less than 3 ⁇ m.
  • the mixture was aggregated for approximately 110 min until the mean aggregate size reached 6.9 ⁇ m.
  • the shell resin an additional 7.69 kg of a styrene-butyl acrylate resin in a latex emulsion
  • the growth of the particles was stopped by the addition of sodium hydroxide until the slurry reached a pH of about 5.5. Then, the batch target temperature was raised to 96 °C.
  • downstream operations included sieving of the slurry to remove the oversize particles that may have been formed due to the high temperature in the reactor, washing the particles to remove surfactants or other ionic species that may impart undesired charging properties, and removing excess moisture by drying the particles.
  • the dry particles were then blended with various surface additives to impart the desired charging characteristics of the toner.
  • the surface additives used were the same as those used in Example 1.
  • a no-wax toner was prepared by an emulsion aggregation process.
  • a reactor was initially charged with 29.6 kg of de-ionized water, 16.8 kg of a styrene-butyl acrylate resin in a latex emulsion, 0.71 kg of a Cyan pigment dispersion, and 1.36 kg of a carbon black pigment dispersion.
  • the contents of the reactor were mixed, and then 1.39 kg of an acid solution with polyaluminum chloride agglomerating agent was added to the reactor. After the agglomerating agent solution was added to the reactor, all of the components in the reactor were homogenized for 10 min or until the size of the particles in the dispersion was less than 3 ⁇ m.
  • the mixture was aggregated for approximately 110 min until the mean aggregate size reached 6.9 ⁇ m.
  • the shell resin an additional 7.69 kg of a styrene-butyl acrylate resin in a latex emulsion
  • the growth of the particles was stopped by the addition of sodium hydroxide until the slurry reached a pH of about 5.5.
  • the batch target temperature was raised to 96 °C. When the slurry reached a temperature of 80 °C, nitric acid was added until a pH of 5.0 was achieved.
  • the temperature of the slurry was maintained, and the circularity of the particles was monitored over time.
  • the pH of the slurry was adjusted to 6.3 by adding sodium hydroxide.
  • the temperature of the slurry was lowered to 53 °C at a rate of 0.6 °C/min.
  • the temperature of the slurry reached 53 °C its pH was adjusted by the addition of sodium hydroxide until the pH of the slurry reached a value of 8.8.
  • These operations included sieving of the slurry to remove the oversize particles that may have been formed due to the high temperature in the reactor, washing the particles to remove surfactants or other ionic species that may impart undesired charging properties, and removing excess moisture by drying the particles.
  • the dry particles were then blended with various surface additives to impart the desired charging characteristics of the toner.
  • the surface additives used were the same as those used in Example 1.
  • Toner formulations of Examples 1-5 are summarized in Table 1, below. Table 1. Toner formulations. Toner Formulation Wax Type Wax Amount (% by weight of toner) Example 1 Paraffin (T m 75 °C) 11.28 Example 2 Paraffin (T m 75 °C) 9.00 Example 3 Polymethylene (T m 92 °C) 11.28 Example 4 Polymethylene (T m 92 °C) 9.00 Example 5 - -
  • the rate of UFP emissions from toners made according to Examples 1 through 5 was measured using a P-TRak Ultra Fine Particle Analyzer manufactured by TSI operated according to the manufacturer's instructions. The same procedure was used for all toner preparations. 100 grams of toner were placed in a glass vial with a sparge tube attached at the top. A heating block was placed on a hot plate with a thermometer measuring the heating block temperature. The hot plate was turned on and the temperature dial set to a nominal value to control the rate of temperature rise of the heating block. When the temperature of the heating block reached 80 °C, the vial was inserted into the block to allow the toner sample to melt.
  • the particle counter was connected to the outlet of the sparge tube at the top of the glass vial containing the toner sample.
  • the timer was started and the particle count reads from the device were captured at 4 °C intervals until the temperature reached 200 °C.
  • the particle counts and temperature data were used to generate the plot of FIG. 1 . Toners were tested both blended with surface additives and without. The presence of the surface additives had no significant effect on the results.
  • T UFP onset The temperature at which the particle count begins to rise above zero is termed as the UFP onset temperature (T UFP onset).
  • T UFP onset can vary. Consequently, the curves for different toners are shifted relative to each other. Curves that are shifted to higher temperatures (i.e., higher values for T UFP onset) are desirable since this signifies that UFPs are released at relatively higher temperatures under the same set of conditions. In other words, at the same fuser temperature, toner with higher T UFP onset and right shifted curves emit lower UFPs.
  • the no wax toner (Example 5) has the highest T UFP onset. In other words, this toner emits the lowest UFPs at any given temperature.
  • Both Examples 3 and 4 (with polymethylene wax) have T UFP onsets which are higher than those of Examples 1 and 2 (with paraffin wax).
  • T m polymethylene wax as a replacement for paraffin wax lowers the overall emission of UFPs.
  • using a lower concentration slightly improves (i.e., increases) T UFP onset. It is clear from the data that compared to the toner having 11.28% paraffin, the toner having 9.00% polymethylene wax exhibits the greatest improvement in UFP performance.
  • the rate of Ultra Fine Particle emissions from Example 1 and Example 4 toners was evaluated after running them in a xerographic printing device that currently uses Example 1 toner.
  • the xerographic printing device was a Monochrome printing device operating at 50 prints per minute.
  • the test procedure and determination of PER 10 (total UFP particles released in a 10 min print phase) follows that described by The Blue Angel (a German certification for products meeting certain environmental standards). See M. Barthel et al., "Measurement of Fine and Ultrafine Particles from Office Devices during Printing in order to Develop a Test Method for the Blue Angel Ecolabel for Office-Based Printing Devices," Texte 75/2013, boombundetics, August 2013 .
  • PER 10 A summary of the determination of PER 10 follows. Modelling of an aerosol (i.e., emitted ultrafine particles) measurement in an emission test chamber can assume simplified conditions with good approximation. The primary measurement is the accumulated particle number concentration C p (t) in a specified particle size range. Absolute level and dynamics of C p (t) are essentially determined by the following factors: source strength of the printing device, chamber size, and particle losses in the chamber, primarily through the air exchange rate.
  • the source strength of the printing device is influenced by its specific product features and the printing activity (length, number of pages and print mode). For different device-specific printing activities, a product comparison requires the standardization of the length of the printing activity, the number of printed pages or other benchmarks.
  • the size of the chamber decides which concentration range should be measured within the detection limits C p (t).
  • Particle losses in the chamber can be described by particle loss rate ⁇ by adjusting a chamber response function of the type R t ⁇ e ⁇ ⁇ t to C p (t) after the end of the emissions.
  • the source strength can be calculated as rate PER(t), (particles emitted per unit of time).
  • C p (t) and PER(t) are linked via a convolution integral, which contains the response function R(t):
  • rate PER(t) can be determined analytically in [particles/unit time] by deconvoluting the convolution integral.
  • the time derivative can be determined numerically.
  • PER t V ch ⁇ dC p t dt ⁇ ⁇ ⁇ C p t
  • PER t V ch ⁇ C p t ⁇ C p t ⁇ ⁇ t ⁇ exp ⁇ ⁇ t ⁇ t ⁇ exp ⁇ ⁇ t ⁇ t ⁇ exp ⁇ ⁇ t
  • Equations (3) and (3a) are mathematically equivalent and contain only known quantities such as the chamber volume V ch and Cp(t).
  • ⁇ t is the time difference between two successive data points.
  • Time t start marks the start of the printing phase and time t stop marks the decline of the emission rate to zero or below a selectable limit.
  • the value of TP can be taken from the integral curve of TP versus time at the point t stop or numerically calculated according to Equation 4.
  • the end of particle emission, t stop is not always identical to the end of the printing activity but must be determined from the curve of the particle emission rate PER(t) before the calculation of TP.
  • the emission time is determined by the difference t stop ⁇ t start
  • TP provides a benchmark for quantitative analysis of particulate emissions.
  • TP may be related to the number of printed pages which defines the benchmark TP / pp [-] (pp stands for printed pages).
  • Alternative definitions of benchmarks are possible.
  • Equation 6 t print [min] stands for the actual duration of the printing activity.
  • Example 1 The results of the machine UFP testing for the Example 1 and Example 4 toners are shown in Table 3, below. Table 3. Machine UFP Test Results. Toner PER 10 Replicate 1 Replicate 2 Average Example 1 3.71 x 10 11 1.59 x 10 11 2.65 x 10 11 Example 4 6.25 x 10 10 3.78 x 10 10 5.01 x 10 10
  • MFT Minimum Fixing Temperature
  • HAT Hot Offset Temperature
  • the MFT of Example 1 was 145 °C; the MFT of Example 2 was 149 °C; the MFT of Example 3 was 154 °C; and the MFT of Example 4 was 155 °C.
  • the hot offset temperature (HOT) is that temperature at which toner that has contaminated the fuser roll is seen to transfer back onto paper. To observe it a blank piece of paper, a chase sheet, is sent through the fuser right after the print with the fused image. If an image offset is notice on the blank chase sheet at a certain fuser temperature then this is the hot offset temperature.
  • the toner of Examples 1-4 exhibited a HOT of greater than 195 °C and none exhibited hot offset over the temperature range of the fuser of the printing device (140 °C to 195 °C).

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Claims (10)

  1. Verfahren zum Herstellen eines Toners, wobei das Verfahren umfasst:
    Ausbilden eines Toners aus einem Gemisch aus wenigstens einem Harz, wenigstens einem Wachs und gegebenenfalls wenigstens einem Farbstoff, wobei der Toner durch einen gemessenen PER10-Wert von nicht mehr als 1 × 1011 Partikel/cm3 gekennzeichnet ist; und
    Messen eines PER10-Wertes für den Toner, wobei der gemessene PER10-Wert für den Toner nicht mehr als 1 × 1011 Partikel/cm3 beträgt, und wobei der PER10-Wert gemäß dem in der Beschreibung offengelegten Verfahren gemessen wird;
    wobei das wenigstens eine Wachs durch ein Tm von wenigstens 90 °C gekennzeichnet ist und die Menge des wenigstens einen Wachses nicht mehr als 10 Gew.-% des Toners beträgt.
  2. Verfahren nach Anspruch 1, bei dem der Schritt des Ausbildens ein Emulsions-Aggregationsvorgang ist.
  3. Verfahren nach Anspruch 1, bei dem der Toner weiterhin gekennzeichnet ist durch eine Minimum-Fix-Temperature im Bereich von 145 °C bis 156 °C, gemessen mit dem Verfahren gemäß der Beschreibung, und/oder eine Hot-Offset-Temperatur von mehr als 195 °C, gemessen mit dem Verfahren gemäß der Beschreibung.
  4. Verfahren nach Anspruch 1, bei dem das wenigstens eine Wachs ausgewählt ist aus Polymethylen, einem Montansäureester, einem Polyethylen und Kombinationen davon und die Menge des wenigstens einen Wachses nicht mehr als 10 Gew.-% des Toners beträgt.
  5. Verfahren nach Anspruch 1, bei dem der Toner aus einem einzigen Wachs besteht.
  6. Verfahren nach Anspruch 5, bei dem das einzige Wachs ausgewählt ist aus Polymethylen, einem Montansäureester und einem Polyethylen und die Menge des einzigen Wachses nicht mehr als 10 Gew.-% des Toners beträgt.
  7. Verfahren nach Anspruch 1, bei dem das wenigstens eine Harz ein Styrol/n-Butylacrylat/ß-CEA-Copolymer ist.
  8. Verfahren nach Anspruch 2, bei dem der Emulsions-Aggregationsvorgang das Aggregieren des Gemisches aus wenigstens einem Harz, wenigstens einem Wachs und gegebenenfalls wenigstens einem Farbstoff zur Bildung aggregierter Partikel, das Auftragen einer Harzbeschichtung auf die aggregierten Partikel zur Bildung einer Schale darüber und das anschließende Koaleszieren der aggregierten Partikel zur Bildung eines Kern-Schale-Toners umfasst.
  9. Verfahren nach Anspruch 1, bei dem das wenigstens eine Harz ein Styrol/n-Butylacrylat/ß-CEA-Copolymer ist; das wenigstens eine Wachs aus Polymethylen, einem Montansäureester, einem Polyethylen und Kombinationen davon ausgewählt ist und die Menge des wenigstens einen Wachses nicht mehr als 10 Gew.-% des Toners beträgt; und der Toner ein Kern-Schale-Toner ist.
  10. Verfahren nach Anspruch 9, bei dem der Toner ein einziges Wachs umfasst und das einzige Wachs Polymethylen oder Polyethylen ist.
EP19155621.6A 2018-02-08 2019-02-05 Verfahren für die herstellung von tonern mit reduzierten emissionen von ultrafeinen partikeln (ufp) Active EP3525043B1 (de)

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JP2019139218A (ja) 2019-08-22
KR20190096279A (ko) 2019-08-19
US20190243271A1 (en) 2019-08-08
KR102404565B1 (ko) 2022-06-02
CA3032781C (en) 2021-09-21
MX2019001377A (es) 2019-08-09
CN110133972A (zh) 2019-08-16
CA3032781A1 (en) 2019-08-08
EP3525043A1 (de) 2019-08-14

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